Beta-nucleating, light stabilizing agents for polypropylene

ABSTRACT

The compounds of the formula (I) wherein R 1  is hydrogen, C 1 -C 8 alkyl, —O, —OH, —CH 2 CN, C 1 -C 13 alkoxy, C 2 -C 16 alkoxy substituted by —OH; C 5 -C 12 cycloalkoxy, C 3 -C 6  alkenyl, C 7 -C 9  phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C 1 -C 4  alkyl; or C 1 -C 8  acyl; R 2  is hydrogen or methyl; R 3  and R 4  are hydrogen or methyl; X is C 2 -C 20 ,alkylene or a group of the formula (II-a-1) (II-a-2) (II-a-3) (II-b-1) (II-b-2) or (II-b-3) and Y is C 5 -C 12 cycloalkyl, C 5 -C 12 cycloalkyl substituted by 1, 2 or 3 C 1 -C 4  alkyl; or a group of the formula (III) wherein R 1  R 2 , R 3  and R 4  are as defined above, are suitable as B-nucleating, light stabilizing agents for polypropylene resins.

The present invention relates to a composition containing a crystallinepolypropylene resin and one or more sterically hindered aminederivatives capable of acting as light stabilizers and nucleating agentsfor the formation of the β-crystal form, to the use of these derivativesas light stabilizing, β-nucleating agents and to articles made from apolypropylene resin containing the β-form crystals.

It is known that crystalline polypropylene may occur in α, β, γ and δcrystal forms as well as in the smectic crystal form which is formed onquenching of melted polypropylene. The β-crystal form (hereinafterreferred to as “β-form”) differs from the more common α-form which isfound, for instance, in the conventional natural pellets in that it islower in melting point and in density, not to speak of differences inthe mode of crystallization and of fracture, thus being of interest fromapplication points of view (Kobunshi Kagaku 30, 694-698, (1973)).

The β-form of polypropylene is less stable compared with thecorresponding α-form under usual processing conditions. When melts ofpolypropylene are extruded and then cooled the α-form of polypropylenetends to predominate. However, polypropylene containing high contents ofthe β-form can be prepared by the addition of a suitable nucleatingagent which induces the formation of the β-form when the polypropyleneis molten and subsequently cooled.

U.S. Pat. No. 6,235,823 describes for example the use of diamidecompounds as β-nucleating agents. Not any nucleating agent forpolypropylene resins does necessarily induce the formation of theβ-crystal form.

EP-A-632,095 describes porous stretched articles of β-crystallinepolypropylene-based resins.

GB-A-1,492,494 describes derivatives of 4-aminopiperidine.

U.S. Pat. No. 4,692,486 describes synergistic mixtures of low-molecularand high-molecular polyalkylpiperidines.

β-Nucleating agents are described in EP-A-557,721.

WO-A-021053,633 discloses a method for making stabilized polyamidecompositions.

Polypropylene compositions containing a β-nucleating agent are describedin EP-A-887,375.

A process for forming a dye image is described in U.S. Pat. No.4,797,350.

Thermoplastic resins are described in DE-A-19,607,203.

JP-A-Hei 09/041,217 describes the production of polyamide fiber havingroughened surface.

U.S. Pat. No. 6,010,819 discloses a method for improving light fastnessof an image.

The present invention relates in particular to a light stabilizedcomposition containing

(1) a crystalline polypropylene resin and

(2) one or more β-nucleating, light stabilizing agents of the formula(I),

wherein

R₁ is hydrogen, C₁-C₈alkyl, —O., —OH, —CH₂CN, C₁-C₁₈alkoxy, C₂-C₁₈alkoxysubstituted by —OH;

C₅-C₁₂cycloalkoxy, C₃-C₆alkenyl, C₇-C₉phenylalkyl unsubstituted orsubstituted on the phenyl by 1, 2 or 3 C₁-C₄alkyl; or C₁-C₈acyl;

R₂ is hydrogen or methyl;

R₃ and R₄ are hydrogen or methyl;

X is C₂-C₁₀alkylene or a group of the formula (II-a-1), (II-a-2),(II-a-3), (II-b-1), (II-b-2) or (II-b-3); and

Y is C₅-C₁₂cycloalkyl, C₅-C₁₂cycloalkyl substituted by 1, 2 or 3C₁-C₄alkyl; or a group of the formula (III)

wherein R₁, R₂, R₃ and R₄ are as defined above,

characterized in that the polypropylene resin of component (1) has acontent of β-form crystals of at least 5% calculated by means of thefollowing equationβ-form crystal content (%)=100×P _(β1)/(P _(α1) +P _(α2) +P _(α3) +P_(β1))

where P_(α1) to P_(α3) are respective peak heights (maxima) of theα-form and P_(β1) is a peak height (maximum) of the β-form determined bywide angle X-ray scattering.

P_(β1) is a reflection intensity (height) on (300) plane of β-formcrystal.

P_(α1) is a reflection intensity (height) on (110) plane of α-formcrystal.

P_(α2) is a reflection intensity (height) on (040) plane of α-formcrystal.

P_(α3) is a reflection intensity (height) on (130) plane of α-formcrystal.

The β-form crystal content may be determined as described by A. TurnerJones et al. in Makromol. Chem. 75, 134 (1964) or as described in U.S.Pat. No. 5,491,188.

In the crystalline polypropylene resin, 5% or more of β-form crystalcontent determined by wide angle X-ray scattering has to be found in atleast one direction.

A preferred embodiment of the present invention relates to a lightstabilized composition wherein the β-form crystals of component (1) aresolidified and/or annealed at ambient temperature or at temperatures(T_(S))T _(S) ≦T _(cr)+35° C.

T_(cr) being the recrystallization temperature of the polypropyleneresin (component (1)) without a β-nucleating agent as determined bydifferential scanning calorimetry (DSC) by cooling the moltenpolypropylene resin at a cooling rate of 10 K/min.

Examples of suitable solidifying and/or annealing temperatures T_(S)are:

(T_(cr) minus 120° C.) to (T_(cr) plus 35° C.)

(T_(cr) minus 100° C.) to (T_(cr) plus 35° C.)

(T_(cr) minus 80° C.) to (T_(cr) plus 35° C.)

(T_(cr) minus 60° C.) to (T_(cr) plus 35° C.)

(T_(cr) minus 40° C.) to (T_(cr) plus 35° C.)

(T_(cr) minus 20° C.) to (T_(cr) plus 35° C.)

(T_(cr) to (T_(cr) plus 35° C.)

(T_(cr) minus 150° C.) to (T_(cr) minus 100° C.)

(T_(cr) minus 120° C.) to (T_(cr) minus 80° C.)

(T_(cr) minus 120° C.) to (T_(cr) minus 60° C.)

(T_(cr) minus 120° C.) to (T_(cr) minus 40° C.)

(T_(cr) minus 120° C.) to (T_(cr) minus 20° C.)

(T_(cr) minus 120° C.) to T_(cr)

(T_(cr) minus 90° C.) to (T_(cr) minus 80° C.)

(T_(cr) minus 90° C.) to (T_(cr) minus 60° C.)

(T_(cr) minus 90° C.) to (T_(cr) minus 40° C.)

(T_(cr) minus 90° C.) to (T_(cr) minus 20° C.)

(T_(cr) minus 90° C.) to T_(cr)

The following solidifying and/or annealing temperatures T_(S) arepreferred:

(T_(cr) minus 80° C.) to (T_(cr) minus 60° C.)

(T_(cr) minus 80° C.) to (T_(cr) minus 40° C.)

(T_(cr) minus 80° C.) to (T_(cr) minus 20° C.)

The following solidifying and/or annealing temperatures T_(S) areparticularly preferred:

(T_(cr) minus 120° C.) to (T_(cr) minus 100° C.)

(T_(cr) minus 110° C.) to (T_(cr) minds 80° C.)

(T_(cr) minus 110° C.) to (T_(cr) minus 90° C.)

(T_(cr) minus 80° C.) to (T_(cr) minus 60° C.)

(T_(cr) minus 40° C.) to (T_(cr) minus 20° C.)

(T_(cr) minus 60° C.) to (T_(cr) minus 40° C.)

(T_(cr) minus 20° C.) to (T_(cr) plus 10° C.)

T_(cr) to (T_(cr) plus 35° C.)

Also of interest are:

(T_(cr) minus 70° C.) to (T_(cr) plus 20° C.)

(T_(cr) minus 60° C.) to (T_(cr) plus 10° C.)

Examples of alkyl having up to 8 carbon atoms are methyl, ethyl, propyl,isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl,n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethyl-butyl, n-hexyl,1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl,1-methylheptyl, 3-methylheptyl, n-octyl and 2-ethylhexyl.

One of the preferred meanings of R₁ is C₁-C₄alkyl, in particular methyl.

Examples of alkoxy having up to 18 carbon atoms are methoxy, ethoxy,propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy,heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy andoctadecyloxy.

One of the preferred meanings of R₁ is C₁-C₁₀alkoxy, in particularmethoxy, propoxy and octoxy.

An example of C₂-C₁₈alkoxy substituted by —OH is —O—CH₂—C(CH₃)₂OH.

Examples of C₅-C₁₂cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl and cyclododecyl. C₅-C₈Cycloalkyl, especially cyclohexyl, ispreferred.

C₅-C₁₂cycloalkyl substituted by 1, 2 or 3 C₁-C₄alkyl is for examplemethylcyclohexyl or dimethylcyclohexyl.

Examples of C₅-C₁₂cycloalkoxy are cyclopentoxy, cyclohexoxy,cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy.C₅-C₈Cycloalkoxy, in particular cyclopentoxy and cyclohexoxy, ispreferred.

Examples of C₇-C₉phenylalkyl are benzyl and phenylethyl.

C₇-C₉Phenylalkyl which is substituted on the phenyl radical by 1, 2 or 3C₁-C₄alkyl is for example methylbenzyl, dimethylbenzyl, trimethylbenzylor tert-butylbenzyl.

Examples of alkenyl having up to 6 carbon atoms are allyl, 2-methallyl,butenyl, pentenyl and hexenyl. Allyl is preferred. The carbon atom inposition 1 is preferably saturated.

Examples of acyl containing not more than 8 carbon atoms are formyl,acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl,acryloyl, methacryloyl and benzoyl. C₁-C₈Alkanoyl, C₃-C₈alkenyl andbenzoyl are preferred. Acetyl and acryloyl are especially preferred.

Examples of alkylene having up to 10 carbon atoms are methylene,ethylene, propylene, trimethylene, tetramethylene, pentamethylene,2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene,octamethylene and decamethylene.

R₁ is preferably hydrogen, C₁-C₄alkyl, C₁-C₁₀alkoxy, cyclohexyloxy,allyl, benzyl or acetyl, in particular hydrogen or methyl.

R₂, R₃ and R₄ are preferably hydrogen.

Y is preferably cyclohexyl or a group of the formula (III).

According to a preferred embodiment of the present invention, R₁ ishydrogen or methyl, R₂, R₃ and R₄ are hydrogen, and Y is a group of theformula (III).

X is preferably a group of the formula (II-a-1) or (II-a-2).

The polypropylene resin of component (1) has preferably a content ofβ-form crystals of 10 to 98%, in particular 15 to 80%.

Further examples of a suitable content of the A-form crystals are,depending on the desired application of the polypropylene resin, 5 to95%, 5 to 90%, 5 to 85%, 5 to 80%, 5 to 75%, 5 to 70%, 5 to 65%, 5 to60%, 5 to 55%,5 to 50%,5 to 45%, 5 to 40%, 5 to 35%, 5 to 30%, 10 to95%, 10 to 90%, 10 to 85%, 10 to 80%, 10 to 75%, 10 to 70%, 10 to 65%,10 to 60%, 10 to55%, 10 to 50%, 10 to 45%, 10 to 40%, 10 to 35%, 10 to30%, 20 to 95%, 20 to 90%, 20 to 85%, 20 to 80%, 20 to 75%, 20 to 70%,20 to 65%, 20 to 60%, 20 to 55%, 20 to 50%, 20 to 45%, 20 to 40%, 20 to35%, 20 to 30%, 30 to 95%, 30 to 90%, 30 to 85%, 30 to 80%, 30 to 75%,30 to 70%, 30 to 65%, 30 to 60%, 30 to 55%, 30 to 50%, 30 to 45%, 30 to40%, 35 to 95%, 35 to 90%, 35 to 85%, 35 to 80%, 35 to 75%, 35 to 70%,35to 65%, 35 to 60%, 35 to 55%, 35 to 50%, 35 to 45%, 40 to 95%, 40 to90%, 40to 85%, 40 to 80%, 40 to 75%, 40 to 70%, 40 to 65%, 40 to 60%, 40to 55%, 40 to 50%, 45 to 95%, 45 to 90%,45 to 85%,45 to 80%,45 to 75%,45to 70%, 45 to 65%, 45 to 60%, 45to 55, 50 to 95%, 50 to 90%, 50 to 85%,50 to 80%, 50 to 75%, 50to 70%, 50 to 65%, 50 to 60%, 55 to 90%, 55 to85%, 55 to 80%, 55 to 75%, 55 to 70%, 55 to 65%, 60 to 95%, 60 to 90%,60 to 85%, 60 to 80%, 60 to 75%, 60 to 70%, 65 to 95%, 65 to 90%, 65 to85%, 65 to 80%, 70 to 95%, 70 to 90%, 70 to 85% and 70 to 80%.

According to a preferred embodiment of the present invention, thepolypropylene resin has a haze which is greater than 62%, in particulargreater than 70% or 80%; the haze value being measured at a plate,preferably prepared by injection molding, of 1.1-1.2 mm thickness. Thehaze value in a range from 65 to 99%, in particular 70 to 99%, 75 to 99%or 80 to 99% is particularly preferred.

The haze is determined according to ASTM D 1003. Haze is defined as thatpercentage transmitted light which in passing through a specimen (plate)deviates from the incident beam by more than 2.5° on the average.Clarity is evaluated in the angle range smaller than 2.5°. The specimenshall have substantially plane-parallel surfaces free of dust, grease,scratches, and blemishes, and it shall be free of distinct internalvoids and particles.

According to a preferred embodiment of the present invention component(1) is a polypropylene homopolymer.

Polypropylene homopolymer also covers long chain branched polypropylene.

Polypropylene, can be prepared by different methods. Examples aredescribed in the following:

Catalytic polymerization using a catalyst that normally contains one ormore than one metal of groups IVb, Vb, VIb or VIII of the PeriodicTable. These metals usually have one or more than one ligand, typicallyoxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenylsand/or aryls that may be either π- or σ-coordinated. These metalcomplexes may be in the free form or fixed on substrates, typically onactivated magnesium chloride, titanium(III) chloride, alumina or siliconoxide. These catalysts may be soluble or insoluble in the polymerisationmedium. The catalysts can be used by themselves in the polymerisation orfurther activators may be used, typically metal alkyls, metal hydrides,metal alkyl halides, metal alkyl oxides or metal alkyloxanes, saidmetals being elements of groups Ia, IIa and/or IIIa of the PeriodicTable. The activators may be modified conveniently with further ester,ether, amine or silyl ether groups. These catalyst systems are usuallytermed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont),metallocene or single site catalysts (SSC).

According to a further preferred embodiment of the present invention,component (1) is a polypropylene random copolymer, alternating orsegmented copolymer or block copolymer containing one or more comonomersselected from the group consisting of ethylene, C₄-C₂₀-α-olefin,vinylcyclohexane, vinylcyclohexene, C₄-C₂₀alkandiene,C₅-C₁₂cycloalkandiene and norbornene derivatives; the total amount ofpropylene and the comonomer(s) being 100%.

Polypropylene copolymer also covers long chain branched polypropylenecopolymer.

Examples of suitable C₄-C₂₀α-olefins are 1-butene, 1-pentene, 1-hexene,1-heptene, 1-octene, 1nonene, 1-decene, 1-undecene, 1-dodecene,1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and4-methyl-1-pentene.

Examples of suitable C₄-C₂₀alkandienes are hexadiene and octadiene.

Examples of suitable C₅-C₁₂cycloalkandienes are cyclopentadiene,cyclohexadiene and cyclooctadiene.

Examples of suitable norbornene derivatives are5-ethylidene-2-norbornene (ENB), dicyclopentadiene (DCP) andmethylene-domethylene-hexahydronaphthaline (MEN).

A propylene/ethylene copolymer contains for example 50 to 99.9%,preferably 80 to 99.9%, in particular 90 to 99.9%, by weight ofpropylene.

A propylene copolymer wherein the comonomer is a C₉-C₂₀α-olefin such ase.g. 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene,1-hexadecene, 1-octadecene or 1-eicosene; C₉-C₂₀alkandiene,C₉-C₁₂cycloalkandiene or a norbornene derivative such as e.g.5-ethylidene-2-norbornene (ENB) ormethylene-domethylene-hexahydronaphthaline (MEN) contains preferablymore than 90 mol %, in particular 90 to 99.9 mol % or 90 to 99 mol %, ofpropylene.

A propylene copolymer wherein the comonomer is a C₄-C₈α-olefin such ase.g. 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene or4-methyl-1-pentene; vinylcyclohexane, vinylcyclohexene, C₄-C₈alkandieneor C₅-C₈cycloalkandiene contains preferably more than 80 mol %, inparticular 80 to 99.9 mol % or 80 to 99 mol %, of propylene.

Further examples of component (1) are propylene/lisobutylene copolymer,propylene/butadiene copolymer, propylene/cycloolefin copolymer,terpolymers of propylene with ethylene and a diene such as hexadiene,dicyclopentadiene or ethylidene-norbornene; propylene/1-olefincopolymers where the 1-olefin is generated in situ; and propylene/carbonmonoxide copolymers.

According to another preferred embodiment of the present inventioncomponent (1) is a thermoplastic polyolefin (TPO).

Thermoplastic polyolefin (TPO) means in particular elastomers thatexhibit rubber characteristics and are based on polyolefins. These arepreferably copolymers from ethylene and propylene (EPM) or terpolymerscomprising ethylene, propylene and a non-conjugated diene (EPDM) and thelike.

The present invention also relates to a composition which additionallycontains (3) a further polymer, in particular a synthetic polymer,preferably EPDM or EPM; with the proviso that component (3) is differentfrom component (1).

Examples of suitable polymers are

1. Polymers of monoolefins and diolefins, for example polyisobutylene,polybut-i-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane,polyisoprene or polybutadiene, as well as polymers of cycloolefins, forinstance of cyclopentene or norbornene, polyethylene (which optionallycan be crosslinked), for example high density polyethylene (HDPE), highdensity and high molecular weight polyethylene (HDPE-HMW), high densityand ultrahigh molecular weight polyethylene (HDPE-UHMW), medium densitypolyethylene (MDPE), low density polyethylene (LDPE), linear low densitypolyethylene (LLDPE), (VLDPE) and (ULDPE). Polyolefins, i.e. thepolymers of monoolefins exemplified in the preceding paragraph,preferably polyethylene and polypropylene, can be prepared by different,and especially by the following, methods:

-   -   a) radical polymerisation (normally under high pressure and at        elevated temperature).    -   b) catalytic polymerisation using a catalyst that normally        contains one or more than one metal of groups IVb, Vb, VIb or        VIII of the Periodic Table. These metals usually have one or        more than one ligand, typically oxides, halides, alcoholates,        esters, ethers, amines, alkyls, alkenyls and/or aryls that may        be either π- or σ-coordinated. These metal complexes may be in        the free form or fixed on substrates, typically on activated        magnesium chloride, titanium(III) chloride, alumina or silicon        oxide. These catalysts may be soluble or insoluble in the        polymerisation medium. The catalysts can be used by themselves        in the polymerisation or further activators may be used,        typically metal alkyls, metal hydrides, metal alkyl halides,        metal alkyl oxides or metal alkyloxanes, said metals being        elements of groups la, Ila and/or llla of the Periodic Table.        The activators may be modified conveniently with further ester,        ether, amine or silyl ether groups. These catalyst systems are        usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta),        TNZ (DuPont), metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers(e.g. ethylene/norbornene like COC), ethylene/1-olefins copolymers,where the 1-olefin is generated in-situ; propylene/butadiene copolymers,isobutylenefisoprene copolymers, ethylene/vinylcyclohexene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acidcopolymers and their salts (ionomers) as well as terpolymers of ethylenewith propylene and a diene such as hexadiene, dicyclopentadiene orethylidene-norbornene; and mixtures of such copolymers with one anotherand with polymers mentioned in 1) above, for examplepolypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetatecopolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EM), LLDPE/EVA,LLDPE/EAA and alternating or random polyalkylene/carbon monoxidecopolymers and mixtures thereof with other polymers, for examplepolyamides.

4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

Homopolymers and copolymers from 1.)-4.) may have any stereostructureincluding syndiotactic, isotactic, hemi-isotactic or atactic; whereatactic polymers are preferred. Stereoblock polymers are also included.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Aromatic homopolymers and copolymers derived from vinyl aromaticmonomers including styrene, α-methylstyrene, all isomers of vinyltoluene, especially p-vinyltoluene, all isomers of ethyl styrene, propylstyrene, vinyl biphenyl, vinyl naphthalene, and vinyl anthracene, andmixtures thereof. Homopolymers and copolymers may have anystereostructure including syndiotactic, isotactic, hemi-isotactic oratactic; where atactic polymers are preferred. Stereoblock polymers arealso included.

6a. Copolymers including aforementioned vinyl aromatic monomers andcomonomers selected from ethylene, propylene, dienes, nitriles, acids,maleic anhydrides, maleimides, vinyl acetate and vinyl chloride oracrylic derivatives and mixtures thereof, for example styrene/butadiene,styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkylmethacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkylmethacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methylacrylate; mixtures of high impact strength of styrene copolymers andanother polymer, for example a polyacrylate, a diene polymer or anethylene/propylene/diene terpolymer; and block copolymers of styrenesuch as styrene/butadiene/styrene, styrene/isoprene/styrene,styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.

6b. Hydrogenated aromatic polymers derived from hydrogenation ofpolymers mentioned under 6.), especially includingpolycyclohexylethylene (PCHE) prepared by hydrogenating atacticpolystyrene, often referred to as polyvinylcyclohexane (PVCH).

6c. Hydrogenated aromatic polymers derived from hydrogenation ofpolymers mentioned under 6a.).

Homopolymers and copolymers may have any stereostructure includingsyndiotactic, isotactic, hemi-isotactic or atactic; where atacticpolymers are preferred. Stereoblock polymers are also included.

7. Graft copolymers of vinyl aromatic monomers such as styrene orα-methylstyrene, for example styrene on polybutadiene, styrene onpolybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styreneand acrylonitrile (or methacrylonitrile) on polybutadiene; styrene,acrylonitrile and methyl methacrylate on polybutadiene; styrene andmaleic anhydride on polybutadiene; styrene, acrylonitrile and maleicanhydride or maleimide on polybutadiene; styrene and maleimide onpolybutadiene; styrene and alkyl acrylates or methacrylates onpolybutadiene; styrene and acrylonitrile on ethylene/propylene/dieneterpolymers; styrene and acrylonitrile on polyalkyl acrylates orpolyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadienecopolymers, as well as mixtures thereof with the copolymers listed under6), for example the copolymer mixtures known as ABS, MBS, ASA or AESpolymers.

8. Halogen-containing polymers such as polychloroprene, chlorinatedrubbers, chlorinated and brominated copolymer of isobutylene-isoprene(halobutyl rubber), chlorinated or sulfochlorinated polyethylene,copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogen-containing vinylcompounds, for example polyvinyl chloride, polyvinylidene chloride,polyvinyl fluoride, polyvinylidene fluoride, as well as copolymersthereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate or vinylidene chloride/vinyl acetate copolymers.

9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates; polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer; polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12,4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides startingfrom m-xylene diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides, polyetherimids,polyesterimids, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate(PAN) and polyhydroxybenzoates, as well as block copolyether estersderived from hydroxyl-terminated polyethers; and also polyestersmodified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polyketones.

21. Polysulfones, polyether sulfones and polyether ketones.

22. Crosslinked polymers derived from aldehydes on the one hand andphenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

23. Drying and non-drying alkyd resins.

24. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

25. Crosslinkable acrylic resins derived from substituted acrylates, forexample epoxy acrylates, urethane acrylates or polyester acrylates.

26. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, isocyanates, isocyanurates,polyisocyanates or epoxy resins.

27. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic,heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidylethers of bisphenol A and bisphenol F, which are crosslinked withcustomary hardeners such as anhydrides or amines, with or withoutaccelerators.

28. Natural polymers such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, for example cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as rosins and their derivatives.

29. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, Poly-amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latexor latices of carboxylated styrene/butadiene copolymers.

Preferred examples of a blend of components (1) and (3) are blends ofpolypropylene with propylene/ethylene copolymers, propylene/butylenecopolymers, polyethylene, e.g. HDPE or LDPE; polybutene,polyisobutylene, poly-4-methylpentene or alternating or randompolyalkylene/carbon monoxide copolymers.

The amount of the β-nucleating, light stabilizing agent (component (2))to be added to the polypropylene resin is not critical insofar as thedesired effect can be obtained. Generally, it is used in an amounteffective for increasing the content of the β-crystal form. 0.0001 to5%, in particular 0.001 to 2%, 0.05 to 1%, 0.1 to 1% or 0.15 to 1%,relative to the weight of component (1), are suitable.

Thus, the β-nucleating, light stabilizing agent of the invention iscapable of causing a crystalline polypropylene resin to undergotransition to the β-crystal form at a very low level of addition and amolded product having a β-form crystal content as indicated above can beobtained under suitable molding conditions.

Component (3) is preferably present in the composition according to thepresent invention in an amount of 1 to 90%, for example 2 to 80% or 5 to50%, relative to the weight of component (1).

A further embodiment of the present invention is a method for improvingthe light stability of a polypropylene resin and for providing saidpolypropylene resin with a content of β-form crystals of at least 5%calculated by means of the following equationβ-form crystal content (%)=100×P _(β1)/(P _(α1) +P _(α2) +P _(α3) +P_(β1))

where P_(α1) to P_(α3) are respective peak heights (maxima) of theα-form and P_(β1) is a peak height (maximum) of the β-form determined bywide angle X-ray scattering,

which comprises incorporating into the polypropylene resin one or moreβ-nucleating, light stabilizing agents of the formula (I).

Another embodiment of the present invention is the use of a compound ofthe formula (I) as β-nucleating agent for a polypropylene resin.

The resin compositions of the present invention may be prepared bystandard procedures, well known to those skilled in the art, ofcompounding, such as mixing the prescribed components in a conventionalmixer by e.g. dry-blending or solution spraying and melting and kneadingthe mixture with a single- or twin-screw extruder, or the like.

The β-nucleating, light stabilizing agent of the formula (I) can beadded to the polypropylene resin at an optional stage, i.e. eitherduring the polymerization reaction or after the polymer has beenprepared.

To the resin compositions of the present invention, additional materialscan be added in a concentration range that does not adversely affect thebeneficial effects of the invention. These materials may includestabilizers, antioxidants, antibacterial agents, ultraviolet absorbers,thermostabilizers, light stabilizers, neutralizers, antistatic agents,antiblocking agents, heavy metal inactivation agents, flame retardants,lubricants, peroxides, hydrotalcite, foaming agents, elastomers,processing aids, additional nucleating agents, reinforcing matter,plasticizer and the like and mixtures thereof.

More detailed examples of these conventional additives are listed below.

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example 2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol,2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)-disulfide.

1.6. Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-α-methylcyclohexyl)-phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butyl-phenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2α-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tertbutyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

1.7. O-, N- and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate,di-dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy-anilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of β-(3.5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis-(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]-undecane.

1.15. Esters of β-(3.5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide(Naugard®XL-1, supplied by Uniroyal).

1.18. Ascorbic Acid (Vitamin C)

1.19. Aminic antioxidants, for exampleN,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenyl-amine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylamino-methylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetra-methyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenyl-amino)propane,(o-tolyl)biguanide, bis[4(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl-tert-octyidiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- and dialkylatedtert-butyl-tert-octylphenothiazines, a mixture of mono- and dialkylatedtert-octylphenothiazines, N-allylphenothiazine,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis(2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV Absorbers and Light Stabilisers

2.1. 2-(2′-Hydroxyphenyl)benzotriazoles, for example2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol];the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300; [R—CH₂CH₂—COO—CH₂CH₂—], whereR=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl,2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)phenyl]-benzotriazole;2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)phenyl]benzotriazole.

2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxyand 2′-hydroxy-4,4′-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, for example4-tert-butylphenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol,benzoyl resorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methylα-cyano-β-methyl-p-methoxycinnamate, butylα-cyano-β-methyl-p-methoxycinnamate, methylα-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

2.5. Nickel compounds, for example nickel complexes of2,2′-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or 1:2complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

2.6. Oxamides, for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

2.7. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl-phenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritol diphosphite,bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,4-di-cumylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,2,2′,2″-nitrilo-[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite,5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.

The following phosphites are especially preferred:

Tris(2,4-di-tert-butylphenyl)phosphite (Irgafos®168, Ciba-Geigy),tris(nonylphenyl)phosphite,

5. Hydroxylamines, for example N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

6. Nitrones, for example N-benzyl-alpha-phenyinitrone,N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptylnitrone,N-lauryl-alpha-undecyinitrone, N-tetradecyl-alpha-tridecylnitrone,N-hexadecyl-alpha-pentadecyinitrone,N-octadecyl-alpha-heptadecyinitrone,N-hexadecyl-alpha-heptadecylnitrone,N-ocatadecyl-alpha-pentadecylnitrone,N-heptadecyl-alpha-hepta-decyinitrone,N-octadecyl-alpha-hexadecylnitrone, nitrone derived fromN,N-dialkylhydroxyl-amine derived from hydrogenated tallow amine.

7. Thiosynergists, for example dilauryl thiodipropionate or distearylthiodipropionate.

8. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercapto-benzimidazole, zincdibutyidithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

9. Polyamide stabilisers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

10. Basic co-stabilisers, for example melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids, for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or zincpyrocatecholate.

11. Other additives, for example plasticisers, lubricants, rheologyadditives, catalysts, flow-control agents, optical brighteners,flameproofing agents, antistatic agents and blowing agents.

12. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. No. 4,325,863; U.S Pat. No. 4,338,244; U.S. Pat. No. 5,175,312;U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643; DE-A-4316611;DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or3-[4-(2-acetoxyethoxy)-phenyl]-5,7-di-tert-butylbenzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]-benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one.

The weight ratio of the β-nucleating, light stabilizing agent(s)(component (2)) to the conventional additive is for example 1:1000 to100:1, preferably 1:100 to 100:1,1:90 to 90:1, 1:80 to 80:1, 1:70 to70:1, 1:60 to 60:1, 1:50 to 50:1, 1:40 to 40:1, 1:30 to 30:1, 1:20 to20:1, 1:10 to 10:1, 1:5 to 5:1, 1:4 to 4:1, 1:3 to 3:1, 1:2 to 2:1 or1:1. In general, the conventional additive is present in the compositionof this invention in an amount of preferably 0.0001 to 5% or 0.001 to3%, in particular 0.01 to 2% or 0.01 to 0.25%, relative to the weight ofcomponent (1).

The polypropylene resin of component (I) preferably contains one or moreprocess stabilizers, e.g. in an amount of 0.001 to 2%, relative to theweight of component (1).

Examples of processing of the resin compositions according to thepresent invention are: Injection blow molding, extrusion, blow molding,rotomolding, in mold decoration (back injection), slush molding,injection molding, co-injection molding, forming, compression molding,pressing, film extrusion (cast film; blown film), fiber spinning (woven,non-woven), drawing (uniaxial, biaxial), annealing, deep drawing,calandering, mechanical transformation, sintering, coextrusion, coating,lamination, crosslinking (radiation, peroxide, silane), vapordeposition, weld together, glue, vulkanization, thermoforming, pipeextrusion, profile extrusion, sheet extrusion; sheet casting, spincoating, strapping, foaming, recycling/rework, extrusion coating,visbreaking (peroxide, thermal), fiber melt blown, spun bonded, surfacetreatment (corona discharge, flame, plasma), sterilization (by gammarays, electron beams), gel-coating, tape extrusion, SMC-process orplastisol.

The resulting crystalline polypropylene resin composition of the presentinvention are preferably molded by injection, compression, blow molding,roto molding and/or other known molding techniques utilizing theconventional molding machines. Molding conditions may be those commonlyemployed. Typical preferred molding conditions may be as follows.Injection molding: resin temperature about 180 to 320° C., preferablyabout 200 to 300° C.; mold temperature about 0 to 120° C., preferablyabout 30 to 80° C. Blow molding: resin temperature about 180 to 300° C.,preferably about 200 to 280° C.; mold temperature about 20 to 140° C.,preferably about 60 to 120° C. Compression molding: temperature ofmelted resin about 180 to 300° C., preferably about 200 to 280° C.;cooling temperature about 10 to 125° C., preferably about 30 to 100° C.

Molded products, which contain much higher proportion of β-crystal formthan the reference material and which are satisfactory in the aspect ofcolor, can be easily obtained by molding under the above-mentionedmolding condition the resin composition of the invention prepared withuse of, for instance, the above-mentioned mixing method. Compared withthe conventional polypropylene pellet which normally does notsubstantially contain β-crystals but is predominantly composed ofα-crystals, the polypropylene molded product has a lower melting pointand requires a lower force for deformation under heating. Therefore, themolded products contribute a great deal to improved secondaryprocessability and mechanical characteristics. The products encompass awide variety of forms such as packaging, containers, bumpers, housing,technical article (e.g. gear) and so on.

With the resin compositions of the present invention, the ratio of α- toβ-form in the final product can be controlled as desired by suitablesolidification conditions. It is possible to control the ratio of α- toβ-form by appropriately selecting cooling conditions under the abovemolding condition. This characteristic is beneficial particularly in thesurface roughening of, for instance, biaxially oriented films andfibres. The film having such a roughened surface displays excellentantiblocking property, printability and adhesion, etc. and is of greatuse in the fields of packaging film, printing paper, tracing paper,oil-immersion type plastic capacitors and so on.

The resin compositions according to the present invention can beadvantageously used for the preparation of various shaped articles.Examples are:

I-1) Floating devices, marine applications, pontoons, buoys, plasticlumber for decks, piers, boats, kayaks, oars, and beach reinforcements.

I-2) Automotive applications, in particular bumpers, dashboards,battery, rear and front linings, moldings parts under the hood, hatshelf, trunk linings, interior linings, air bag covers, electronicmoldings for fittings (lights), panes for dashboards, headlamp glass,instrument panel, exterior linings, upholstery, automotive lights, headlights, parking lights, rear lights, stop lights, interior and exteriortrims; door panels; gas tank; glazing front side; rear windows; seatbacking, exterior panels, wire insulation, profile extrusion forsealing, cladding, pillar covers, chassis parts, exhaust systems, fuelfilter/filler, fuel pumps, fuel tank, body side mouldings, conyertibletops, exterior mirrors, exterior trim, fasteners/fixings, front endmodule, glass, hinges, lock systems, luggage/roof racks, pressed/stampedparts, seals, side impact protection, sound deadener/insulator andsunroof.

I-3) Road traffic devices, in particular sign postings, posts for roadmarking, car accessories, warning triangles, medical cases, helmets,tires.

I-4) Devices for plane, railway, motor car (car, motorbike) includingfurnishings.

I-5) Devices for space applications, in particular rockets andsatellites, e.g. reentry shields.

I-6) Devices for architecture and design, mining applications, acousticquietized systems, street refuges, and shelters.

II-1) Appliances, cases and coverings in general and electric/electronicdevices (personal computer, telephone, portable phone, printer,television-sets, audio and video devices), flower pots, satellite TVbowl, and panel devices.

II-2) Jacketing for other materials such as steel or textiles.

II-3) Devices for the electronic industry, in particular insulation forplugs, especially computer plugs, cases for electric and electronicparts, printed boards, and materials for electronic data storage such aschips, check cards or credit cards.

II-4) Electric appliances, in particular washing machines, tumblers,ovens (microwave oven), dish-washers, mixers, and irons.

II-5) Covers for lights (e.g. street-lights, lamp-shades).

II-6) Applications in wire and cable (semi-conductor, insulation andcable-jacketing).

II-7) Foils for condensers, refrigerators, heating devices, airconditioners, encapsulating of electronics, semi-conductors, coffeemachines, and vacuum cleaners.

III-1) Technical articles such as cogwheel (gear), slide fittings,spacers, screws, bolts, handles, and knobs.

III-2) Rotor blades, ventilators and windmill vanes, solar devices,swimming pools, swimming pool covers, pool liners, pond liners, closets,wardrobes, dividing walls, slat walls, folding walls, roofs, shutters(e.g. roller shutters), fittings, connections between pipes, sleeves,and conveyor belts.

III-3) Sanitary articles, in particular shower cubicles, lavatory seats,covers, and sinks.

III-4) Hygienic articles, in particular diapers (babies, adultincontinence), feminine hygiene articles, shower curtains, brushes,mats, tubs, mobile toilets, tooth brushes, and bed pans.

III-5) Pipes (cross-linked or not) for water, waste water and chemicals,pipes for wire and cable protection, pipes for gas, oil and sewage,guttering, down pipes, and drainage systems.

III-6) Profiles of any geometry (window panes) and siding.

III-7) Glass substitutes, in particular extruded plates, glazing forbuildings (monolithic, twin or multiwall), aircraft, schools, extrudedsheets, window film for architectural glazing, train, transportation,sanitary articles, and greenhouse.

III-8) Plates (walls, cutting board), extrusion-coating (photographicpaper, tetrapack and pipe coating), silos, wood substitute, plasticlumber, wood composites, walls, surfaces, furniture, decorative foil,floor coverings (interior and exterior applications), flooring, duckboards, and tiles.

III-9) Intake and outlet manifolds.

III-10) Cement-, concrete-, composite-applications and covers, sidingand cladding, hand rails, banisters, kitchen work tops, roofing, roofingsheets, tiles, and tarpaulins.

IV-1) Plates (walls and cutting board), trays, artificial grass,astroturf, artificial covering for stadium rings (athletics), artificialfloor for stadium rings (athletics), and tapes.

IV-2) Woven fabrics continuous and staple, fibers (carpets/hygienicarticles/geotextiles/monofilaments; filters; wipes/curtains(shades)/medical applications), bulk fibers (applications such asgown/protection clothes), nets, ropes, cables, strings, cords, threads,safety seat-belts, clothes, underwear, gloves; boots; rubber boots,intimate apparel, garments, swimwear, sportswear, umbrellas (parasol,sunshade), parachutes, paraglides, sails, “balloon-silk”, campingarticles, tents, airbeds, sun beds, bulk bags, and bags.

IV-3) Membranes, insulation, covers and seals for roofs, tunnels, dumps,ponds, dumps, walls roofing membranes, geomembranes, swimming pools,curtains (shades)/sun-shields, awnings, canopies, wallpaper, foodpacking and wrapping (flexible and solid), medical packaging (flexible &solid), airbags/safety belts, arm and head rests, carpets, centreconsole, dashboard, cockpits, door, overhead console module, door trim,headliners, interior lighting, interior mirrors, parcel shelf, rearluggage cover, seats, steering column, steering wheel, textiles, andtrunk trim.

V) Films (packaging, dump, laminating, agriculture and horticulture,greenhouse, mulch, tunnel, silage), bale wrap, swimming pools, wastebags, wallpaper, stretch film, raffia, desalination film, batteries, andconnectors.

VI-1) Food packing and wrapping (flexible and solid), BOPP, BOPET,bottles.

VI-2) Storage systems such as boxes (crates), luggage, chest, householdboxes, pallets, shelves, tracks, screw boxes, packs, and cans.

VI-3) Cartridges, syringes, medical applications, containers for anytransportation, waste baskets and waste bins, waste bags, bins, dustbins, bin liners, wheely bins, container in general, tanks forwater/used water/chemistry/gas/oil/gasoline/diesel; tank liners, boxes,crates, battery cases, troughs, medical devices such as piston,ophthalmic applications, diagnostic devices, and packing forpharmaceuticals blister.

VII-1) Extrusion coating (photo paper, tetrapack, pipe coating),household articles of any kind (e.g. appliances, thermos bottle/clotheshanger), fastening systems such as plugs, wire and cable clamps,zippers, closures, locks, and snap-closures.

VII-2) Support devices, articles for the leisure time such as sports andfitness devices, gymnastics mats, ski-boots, inline-skates, skis, bigfoot, athletic surfaces (e.g. tennis grounds); screw tops, tops andstoppers for bottles, and cans.

VII-3) Furniture in general, foamed articles (cushions, impactabsorbers), foams, sponges, dish clothes, mats, garden chairs, stadiumseats, tables, couches, toys, building kits (boards/figures/balls),playhouses, slides, and play vehicles.

VII-4) Materials for optical and magnetic data storage.

VII-5) Kitchen ware (eating, drinking, cooking, storing).

VII-6) Boxes for CD's, cassettes and video tapes; DVD electronicarticles, office supplies of any kind (ball-point pens, stamps andink-pads, mouse, shelves, tracks), bottles of any volume and content(drinks, detergents, cosmetics including perfumes), and adhesive tapes.

VII-7) Footwear (shoes/shoe-soles), insoles, spats, adhesives,structural adhesives, food boxes (fruit, vegetables, meat, fish),synthetic paper, labels for bottles, couches, artificial joints (human),printing plates (flexographic), printed circuit boards, and displaytechnologies.

VII-8) Devices of filled polymers (talc, chalk, china clay (kaolin),wollastonite, pigments, carbon black, TiO₂, mica, nanocomposites,dolomite, silicates, glass, asbestos).

Thus, a further embodiment of the present invention relates to a shapedarticle, in particular a film fiber, profile, pipe, bottle, tank orcontainer, containing a resin composition as described above.

A molded article is preferred. The molding is in particular effected byinjection, blow, compression, roto-molding or slush-molding orextrusion.

A further embodiment of the present invention relates to amonoaxially-oriented film or a biaxially-oriented film which has beenformed by stretching a film containing a composition as described above.

Another embodiment of the present invention is a fiber which has beenformed by stretching a fiber containing a composition as describedabove.

The present invention further relates to a multilayer system in whichone or more layers contain a composition as described above.

The compounds of the formula (I) can be prepared in analogy to knownprocesses such as described in the working examples.

A further embodiment of the present invention relates to the novelcompounds of the formula (I-A)

wherein

R₁ is hydrogen, C₁-C₈alkyl, —O., —OH, —CH₂CN, C₁-C₁₈alkoxy, C₂-C₁₈alkoxysubstituted by —OH;

C₅-C₁₂cycloalkoxy, C₃-C₆alkenyl, C₇-C₉phenylalkyl unsubstituted orsubstituted on the phenyl by 1, 2 or 3 C₁-C₄alkyl; or C₁-C₈acyl;

R₂ is hydrogen or methyl;

R₃ and R₄ are hydrogen or methyl;

X is C₂-C₁₀alkylene or a group of the formula (II-a-1), (II-a-2),(II-a-3), (II-b-1), (II-b-2) or (II-b-3); and

Y is C₅-C₁₂cycloalkyl, C₅-C₁₂cycloalkyl substituted by 1, 2 or 3C₁-C₄alkyl; or a group of the formula (III)

wherein R₁, R₂, R₃ and R₄ are as defined above;

with the proviso that

R₁ is different from hydrogen and —O., when Y is a group of the formula(III) and at the same time X is the group (II-a-1).

Examples of compounds of the formulae (I) and (I-A) are

A further embodiment of the present invention is a compositioncontaining a polymer, preferably a synthetic polymer, susceptible todegradation induced by light, heat or oxidation, and a novel compound ofthe formula (I-A).

Examples of suitable polymers are those listed above for component (3)under times 1 to 30.

Another embodiment of the present invention is a method for stabilizinga polymer, preferably a synthetic polymer, against degradation inducedby light, heat or oxidation, which comprises incorporating into thepolymer a novel compound of the formula (I-A).

The following examples describe the present invention in greater detail.

Unless indicated otherwise, heretofore and hereinafter, all parts andpercentages are by weight and all temperatures are given in degreesCelsius (° C.).

EXAMPLE A Preparation of the Compound of the Formula

A 2.5 l three neck flask equipped with a stirrer, thermometer andcondenser is charged with 153.3 g (1.0 mol) of4-amino-2,2,6,6-tetramethylpiperidine, 12.5 g (0.29 mol) of dry lithiumchloride, 223 g (2.16 mol) of triethylamine and 750 ml ofN-methylpyrrolidone (NMP). The mixture is cooled to 5° C. and a solutionof 76.9 g (0.375 mol) of terephthaloyl chloride in 250 ml of NMP isadded within 30 minutes. The yellow suspension is then heated to 75-80 °C. and stirred for 2 hours. After cooling the reaction mixture is pouredin 3 l of ice water. The precipitate is recovered by filtration anddried under reduced pressure at 100° C. The obtained raw product is thenrecrystallized from 1 l of NMP. The desired product is obtained in formof white crystals.

Yield: 124 g (75% of theory).

Melting point: 330-335° C.

Elemental Analysis for C₂₆H₄₂N₄O₂:

Calculated: C 70.55%, H 9.56%, N 12.66%.

Found: C 70.11%, H 9.45%, N 12.62%.

EXAMPLE B Preparation of the Compound of the Formula

83.75 g (0.26 mole) of 4-amino-2,2,6,6-tetramethylpiperidine aredissolved in 350 ml of N,N-dimethyl formamide, in a 750 ml roundbottomed 3 necked reaction flask with stirrer, thermometer, funnel andreflux-condenser. 30.71 g (0.304 mole) and 8.5 g (0.2 mole) of lithiumchloride are added under constant stirring at room temperature. Thesolution is cooled to 0° C. and during 1 hour 65.8 g (0.26 mole) ofnaphthalene-2,6-dicarbonyl-dichloride are added in small portions undervigourous stirring. A faintly yellow suspension results. The reactionmass is kept at 0-5° C. for 1 hour. Within a further hour, thetemperature is raised to room temperature and then the whole is kept at65° C for further 2 hours. The reaction product is then diluted with 200ml of isopropanol/water (1/4). The reaction mixture is then poured on600 ml of water, under stirring. Then, the solid residue is filtered offand subsequently washed with several portions of isopropanol/water(1/1). Afterwards, the solid is dried in a vacuum drier at 80° C. for 15hours. The desired product is obtained as a colourless powder.

Yield: 76, 1 g (=76% of theory).

Melting-point: higher than 300° C.

EXAMPLE C Preparation of the Compound of the Formula

In analogy to Example A, 9.07 g (0.053 mol) of4-amino-2,2,6,6-tetramethylpiperidineoxide are reacted with 1.7 g (0.041mol) of dry lithium chloride, 30.9 g (0.3 mol) of triethylamine and 4.04g (0.02 mol) of terephthaloyl chloride. The raw product is refluxed in200 ml of methanol. The white suspension is cooled to room temperature,filtered and the residue is dried under vacuum at 80° C. The desiredproduct is obtained in form of a white powder.

Yield: 7.63 g (60.5% of theory).

Melting point: higher than 280° C. (decomposition).

Elemental Analysis for C₂₆H₄₀N₄O₄:

Calculated: C 66.07%, H 8.53%, N 11.85%.

Found: C 65.51%, H 8.61%, N 11.70%.

EXAMPLE D Preparation of the Compound of the Formula

In analogy to Example A, 4.70 g (0.025 mol) of1-methoxy-2,2,6,6-tetramethyl-piperidin-4-ylamine are reacted with 0.8 g(0.019 mol) of dry lithium chloride, 14.2 g (0.14 mol) of triethylamineand 1.90 g (0.01 mol) of terephthaloyl chloride. The raw product isrefluxed in 100 ml of methanol. The white suspension is cooled to roomtemperature, filtered and the residue is dried under vacuum at 80° C.The desired product is obtained in form of a white powder.

Yield: 4.0 g (85% of theory).

Melting Point: higher than 320° C. (decomposition).

Elemental Analysis for C₂₈H₄₆N₄O₄:

Calculated: C 66.90%, H 9.22%, N 11.15%.

Found: C 66.60%, H 9.28%, N 11.05%.

In the Examples Below, the Following Procedures are Applied.

Determination of the β-Form Crystal Content by Wide Angle X-RayScattering (WVAXS):

A Siemens (RTM) wide angle X-ray diffractometer (Model D500) is used forthe analysis of the β-modification content of the specimen prepared asdescribed below. The test specimen is placed in a sample holder in themiddle between the copper K_(α) radiation source (%=1.54178 Å) and thedetector. The sample is rotated during the recording at 2 rpm. Thediffraction pattern is recorded from 2 Θ=5-35° at an increment of 0.025°and a recording time of 1 sec. The β-form crystal content is determinedas described by A. Turner Jones et al., Makromol. Chem. 75, 134 (1964)and in U.S. Pat. No. 5,491,188 according to the following equation:β-form crystal content (%)=100×P _(β1)/(P _(α1) +P _(α2) +P _(α3) +P_(β1))

where P_(α1) to P_(α3) means the maximum peak heights of the α-form andP_(β1) means the maximum peak height of the β-form determined by wideangle X-ray scattering.

P_(β1) is a reflection intensity (height) on (300) plane of deformcrystal.

P_(α1) is a reflection intensity (height) on (110) plane of α-formcrystal.

P_(α2) is a reflection intensity (height) on (040) plane of α-formcrystal.

P_(α3) is a reflection intensity (height) on (130) plane of α-formcrystal.

Differential Scanning Calorimetry (DSC):

A Perkin-Elmer DSC instrument (RTM) (Model DSC 7), operated in a drynitrogen atmosphere, is used for the analysis of the crystallizationbehavior of the various samples, according to standard procedures. About5 to 10 mg of sample is sealed into an aluminum cup, heated from 130° C.to 230° C. at a rate of 10° C./min, held at 230° C. for 5 min, and thensubsequently cooled at a rate of 10° C./min to 50° C. The datarepresented as crystallization temperatures are the peak temperatures ofthe exotherms (predominant peak minimum) in the thermograms that arerecorded upon cooling.

EXAMPLE I

2.5 kg of polypropylene powder (Moplen FL F 20 (RTM) of Montell (RTM))are mixed to homogeneity in a high-speed mixer with 0.10% oftris(2,4-di-tert-butylphenyl)phosphite, 0.05% of pentaerythritoltetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 0.10% ofcalcium stearate and 0.20% of Compound A. This blend is then extruded ina twin-screw extruder of Berstorff (RTM) at a temperature of at most240° C. After drawing the extrudate through a waterbath to cool, it isgranulated.

55 g of the granules are molten at T₁=240° C. for 15 min in a melt pressSuter LP 322 (RTM). Subsequently, the molten polypropylene resincomposition is put in a second melt press (Suter LP 322 (RTM)) which hasa temperature of T₂=110° C. The samples are pressed at p=10 bar and areannealed/crystallized for 60 min at the indicated temperature T_(s). Theβ-form crystal content is shown in Table 1. TABLE 1 Recrystallizationtemperature (T_(cr)) of the polypropylene resin (component (1)) withoutβ-nucleating agent: 112.0° C. β-nucleating agent T_(s) in ° C. β-formcrystal content in % Compound of Example A 110 33

The sample further shows an excellent light stability in aWEATHER-OMETER.

EXAMPLE II

2.5 kg of polypropylene powder (Moplen FL F 20 (RTM) of Montell (RTM))are mixed to homogeneity in a high-speed mixer with 0.10% oftris(2,4-di-tert-butylphenyl)phosphite, 0.05% of pentaerythritoltetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 0.10% ofcalcium stearate and 0.20% of Compound B. This blend is then extruded ina twin-screw extruder of Berstorff (RTM) at a temperature of at most240° C. After drawing the extrudate through a waterbath to cool, it isgranulated.

55 g of the granules are molten at T₁=240° C. for 15 min in a melt pressSuter LP 322 (RTM). Subsequently, the molten polypropylene resincomposition is put in a second melt press (Suter LP 322 (RTM)) which hasa temperature of T₂=100° C. The samples are pressed at p=10 bar and areannealed/crystallized for 30 min at the indicated temperature T_(s). Theβ-form crystal content is shown in Table 2. TABLE 2 β-nucleating agentT_(s) in ° C. β-form crystal content in % Compound of Example B 100 42

The sample further shows an excellent light stability in aWEATHER-OMETER.

EXAMPLE III

Compounding:

5 kg of polypropylene homopolymer (Moplen PH 350 (RTM) of Montell (RTM))powder are mixed to homogeneity in a high-speed mixer with 0.10% oftris(2,4-di-tert-butylphenyl)phosphite, 0.05% of pentaerythritoltetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 0.10% ofcalcium stearate and different amounts of the compound of the formula(I). This blend is then extruded in a twin-screw extruder of Berstorff(RTM) (screw diameter 25 mm, UD ratio: 46) at a temperature of at most230° C. After drawing the extrudate through a water bath to cool, it isgranulated.

Cast Film Preparation:

Cast films are produced by using a single screw extruder (Dr. Collin, E30M) equipped with a cast film line (Dr. Collin CR136/350) attemperatures of 230° C. (extruder) and 115° C. (chill roll). Cast filmsare produced at a thickness of 0.2 mm and 1 mm.

Production of Biaxial Oriented Films:

Test sample preparation: Test samples are cut into 85 mm×85 mm piecesfrom the cast film. Stretching is performed in a biaxial stretchingmachine of Brückner Karo IV at a Hencky strain of 0.1 s⁻¹.

Initial size LO (mm): MD×TD=70×70 (clip distance 70 mm)

Preheating time: 40 sec/150° C.

Set clip temperature: 95° C.

1. A light stabilized composition containing (1) a crystallinepolypropylene resin and (2) one or more β-nucleating, light stabilizingagents of the formula (I),

wherein R₁ is hydrogen, C₁-C₈alkyl, —O., —OH, —CH₂CN, C₁-C₁₈alkoxy,C₂-C₁₈alkoxy substituted by —OH, C₅-C₁₂cycloalkoxy, C₃-C₆alkenyl,C₇-C₉phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3C₁-C₄alkyl, or C₁-C₈acyl; R₂ is hydrogen or methyl; R₃ and R₄ arehydrogen or methyl; X is C₂-C₁₀alkylene or a group of the formula(II-a-1), (II-a-2), (II-a-3), (II-b-1), (II-b-2) or (II-b-3);

and Y is C₅-C₁₂cycloalkyl, C₅-C₁₂cycloalkyl substituted by 1, 2 or 3C₁-C₄alkyl; or a group of the formula (III)

wherein R₁, R₂, R₃ and R₄ are as defined above, characterized in thatthe polypropylene resin of component (1) has a content of β-formcrystals of at least 5% calculated by means of the following equationβ-form crystal content (%)=100×P _(β1)/(P _(α1) +P _(α2) +P _(α3) +P_(β1)) where P_(α1) to P_(α3) are respective peak heights (maxima) ofthe α-form and P_(β1) is a peak height (maximum) of the β-formdetermined by wide angle X-ray scattering.
 2. A light stabilizedcomposition according to claim 1 wherein R₁ is hydrogen, C₁-C₄alkyl,C₁-C₁₀alkoxy, cyclohexyloxy, allyl, benzyl or acetyl.
 3. A lightstabilized composition according to claim 1 wherein R₁ is hydrogen ormethyl.
 4. A light stabilized composition according to claim 1 whereinR₂, R₃ and R₄ are hydrogen.
 5. A light stabilized composition accordingto claim 1 wherein Y is cyclohexyl or a group of the formula (III).
 6. Alight stabilized composition according to claim 1 wherein R₁ is hydrogenor methyl, R₂, R₃ and R₄ are hydrogen, and Y is a group of the formula(III).
 7. A light stabilized composition according to claim 1 wherein Xis a group of the formula (II-a-1) or (II-a-2).
 8. A light stabilizedcomposition according to claim 1, wherein the β-form crystals ofcomponent (1) are solidified and/or annealed at ambient temperature orat temperatures (T_(S))T _(S) ≦T _(cr)+35° C. T_(cr) being the recrystallization temperature ofthe polypropylene resin (component (1)) without a β-nucleating, lightstabilizing agent, as determined by differential scanning calorimetry(DSC) by cooling the molten polypropylene resin at a cooling rate of 10K/min.
 9. A light stabilized composition according to claim 1 whereinthe polypropylene resin of component (1) has a content of deformcrystals of 10 to 98%.
 10. A light stabilized composition according toclaim 1 wherein the polypropylene resin of component (1) has a contentof p-form crystals of 15 to 80%.
 11. A light stabilized compositionaccording to claim 1, which is further characterized in that thepolypropylene resin has a haze which is greater than 62%; the haze valuebeing measured at a plate of 1.1-1.2 mm thickness.
 12. A lightstabilized composition according to claim 1 wherein component (1) is apolypropylene homopolymer.
 13. A light stabilized composition accordingto claim 1 wherein component (1) is a polypropylene random copolymer,alternating or segmented copolymer or block copolymer containing one ormore comonomers selected from the group consisting of ethylene,C₄-C₂₀α-olefin, vinylcyclohexane, vinylcyclohexene, C₄-C₂₀alkanediene,C₅-C₁₂cycloalkandiene and norbornene derivatives.
 14. A light stabilizedcomposition according to claim 1 wherein component (1) is athermoplastic polyolefin (TPO).
 15. A light stabilized compositionaccording to claim 1 which additionally contains (3) a further polymer,with the proviso that component (3) is different from component (1). 16.A method for improving the light stability of a polypropylene resin andfor providing said polypropylene resin with a content of β-form crystalsof at least 5% calculated by means of the following equationβ-form crystal content (%)=100×P _(β1)/(P _(α1) +P _(α2) +P _(α3) +P_(β1)) where P_(α1) to P_(α3) are respective peak heights of the α-form(maxima) and P_(β1) is a peak height (maximum) of the β-form determinedby wide angle X-ray scattering, which method comprises incorporatinginto the polypropylene resin one or more β-nucleating, light stabilizingagents as defined in claim
 1. 17. (canceled)
 18. A shaped articlecontaining a composition according to claim
 1. 19. A shaped articleaccording to claim 18, which is a molded article.
 20. A shaped articleaccording to claim 19, where the molding is effected by injection, blow,compression, roto-molding or slush-molding or extrusion.
 21. A shapedarticle according to claim 18, which is a film, fiber, profile, pipe,bottle, tank or container.
 22. A monoaxially-oriented film or abiaxially-oriented film which has been formed by stretching a filmaccording to claim
 21. 23. A fiber which has been formed by stretching afiber according to claim
 21. 24. A multilayer system in which one ormore layers contain a composition according to claim
 1. 25. A compoundof the formula (I-A)

wherein R₁ is hydrogen, C₁-C₈alkyl, —O., —OH, —CH₂CN, C₁-C₁₈alkoxy,C₂-C₁₈alkoxy substituted by —OH, C₅-C₁₂cycloalkoxy, C₃-C₆alkenyl,C₇-C₉phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3C₁-C₄alkyl, or C₁-C₈acyl; R₂ is hydrogen or methyl; R₃ and R₄ arehydrogen or methyl; X is C₂-C₁₀alkylene or a group of the formula(II-a-1), (II-a-2), (II-a-3), (II-b-1), (II-b-2) or (II-b-3);

and Y is C₅-C₁₂cycloalkyl, C₅-C₁₂cycloalkyl substituted by 1, 2 or 3C₁-C₄alkyl; or a group of the formula (III)

wherein R₁, R₂, R₃ and R₄ are as defined above; with the proviso that R₁is different from hydrogen and —O., when Y is a group of the formula(III) and at the same time X is the group (II-a-1).
 26. A compoundaccording to claim 25 which is


27. A composition containing a polymer susceptible to degradationinduced by light, heat or oxidation, and a compound according to claim25.
 28. A method for stabilizing a polymer against degradation inducedby light, heat or oxidation, which method comprises incorporating intothe polymer a compound according to claim 25.